US4362861A - Polyesterimide - Google Patents

Polyesterimide Download PDF

Info

Publication number
US4362861A
US4362861A US06/311,386 US31138681A US4362861A US 4362861 A US4362861 A US 4362861A US 31138681 A US31138681 A US 31138681A US 4362861 A US4362861 A US 4362861A
Authority
US
United States
Prior art keywords
polyester
imide
electrical conductor
wire
coating composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US06/311,386
Inventor
Dennis C. Shen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SCEHNECTADY CHEMICALS Inc A CORP OF NY
SI Group Inc
Original Assignee
Schenectady Chemicals Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Schenectady Chemicals Inc filed Critical Schenectady Chemicals Inc
Assigned to SCEHNECTADY CHEMICALS, INC., A CORP. OF N.Y. reassignment SCEHNECTADY CHEMICALS, INC., A CORP. OF N.Y. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: SHEN, DENNIS C.
Priority to US06/311,386 priority Critical patent/US4362861A/en
Priority to CA000392277A priority patent/CA1180488A/en
Priority to AR28783181A priority patent/AR227453A1/en
Priority to EP19810305928 priority patent/EP0055085A1/en
Priority to AU78609/81A priority patent/AU543192B2/en
Priority to BR8108351A priority patent/BR8108351A/en
Publication of US4362861A publication Critical patent/US4362861A/en
Application granted granted Critical
Priority to JP17363188A priority patent/JPS6426679A/en
Priority to JP17363088A priority patent/JPS6426678A/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/308—Wires with resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/16—Polyester-imides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
    • H01B3/306—Polyimides or polyesterimides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2942—Plural coatings
    • Y10T428/2947—Synthetic resin or polymer in plural coatings, each of different type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31721—Of polyimide

Definitions

  • the present invention relates to the preparation of novel polyester-imides and their use in coating wires with outstanding physical properties.
  • Example 9 a polyester-imide prepared from ethylene glycol, glycerine and a diimide dicarboxylic acid prepared by reacting two moles of trimellitic anhydride with one mole of methylene dianiline.
  • This diimide dicarboxylic acid is sometimes abbreviated hereinafter as DID.
  • the polymers prepared in Schmidt have a triol to diol molar ratio of 0.676, a hydroxy to carboxy equivalent ratio of 1.41.
  • the product has a 250° C. heat shock without using prestretch of the wire and employing one hour of baking.
  • Terebec FH contains substantial amounts of ester derived from terephthalic acid and a small amount of imide derived from DID.
  • Terebec FH in inferior in properties to the commercial polyester-imide, ISOMID, made in accordance with Meyer U.S. Pat. No. 3,426,098.
  • polyesterimide resins as a top coat for electrical conductors coated with a polyester resin or other resin
  • a polyester resin or other resin e.g., Ishizuka U.S. Pat. No. 4,208,464, Keske U.S. Pat. No. 4,070,524, Czajka U.S. Pat. No. 3,944,706, Keske U.S. Pat. No. 4,012,555, and Keske U.S. Pat. No. 4,012,556.
  • the products of these patents do not have sufficiently good heat shock properties.
  • a number of these patents e.g., the Keske and Czajka patents, are directed to self-bonding coatings for magnet wires.
  • the self-bonding property is incompatible with good heat shock properties.
  • Ishizuka prepares a water soluble polyester-imide having an acid value of 30-50, an OH/COOH equivalent ratio of 1:1 to 2:1 and requires a substantial amount of an aliphatic polycarboxylic acid.
  • polyester-imide having outstanding physical properties when applied to a wire.
  • the new polyester-imide can compete, as a single-coat system, against the amide-imide topcoated polyester (e.g., amide-imide coated ISONEL 200/ system now used in the art).
  • the new polyester-imide passes the A. O. Smith blister test and had good burn-out results.
  • the new polyester-imide employs as the dicarboxylic acid DID or a mixture of DID with a small amount of another aromatic dicarboxylic acid.
  • a polyester-imide is made with a hydroxyl to carboxyl equivalent ratio of 2.65:1 to 3.67:1, preferably 2.65:1 to 3.33:1. The ratio can even be as high as 4.0:1.
  • a polyester-imide is made with trihydric alcohol to dihydric alcohol molar ratio of 0.23:1 to 0.62:1, preferably 0.4:1 to 0.5:1.
  • polyester-imide is made with 40-50%, usually 42.5-50%, by equivalent, imide groups, preferably 45-50%, by equivalent, imide groups.
  • polyester-imide is made with the following mole percentages of ingredients:
  • the molar ratios of the reactants change quite considerably depending on whether one starts with trimellitic anhydride and methylene dianiline on the one hand or prereacts them and then bases the calculation on the preformed DID.
  • Two moles of TMA and one mole of MDA are condensed to become only one mole of DID, thereby changing the molar calculation.
  • the mole percent of THEIC is 23% based on the use of DID, or 15.3% when the MDA and TMA are not prereacted to form DID.
  • THEIC molar percentages are always higher in those cases using prereacted DID, because the DID always involve a fewer number of total moles and therefore the contribution of the THEIC becomes proportionately greater.
  • the polyester-imide normally has an average molecular weight of from 700 to 1300 or even up to 2,000, but preferably an average molecular weight of from 750-1050.
  • the molecular weights were determined by Vapor Pressure Osmometer.
  • the hydroxyl number of the polyester-imide frequently is within 380-420, but this can be varied, e.g., it can be as low as 350 or as high as 450.
  • the polyester-imide is made using (1) tris (2-hydroxyethyl) isocyanurate (THEIC), (2) a dibasic acid such as terephthalic acid (TA) or its lower alkyl esters, e.g., dimethyl terephthalate (DMT), diethyl terephthalate or dibutyl terephthalate, (3) trimellitic anhydride (TMA), (4) a diamine, such as methylene dianiline or oxydianiline, preferably methylene dianiline and (5) a dihydric alcohol such as ethylene glycol.
  • TEEIC tris (2-hydroxyethyl) isocyanurate
  • TA terephthalic acid
  • DMT dimethyl terephthalate
  • TMA trimellitic anhydride
  • a diamine such as methylene dianiline or oxydianiline, preferably methylene dianiline
  • a dihydric alcohol such as ethylene glycol.
  • the polyester-imides of this invention can be cooked at 70-100% concentration in various kinds of solvent media, such as cresylic acid, n-methyl pyrrolidone, ethylene glycol, methyl Carbitol (monomethyl ether of diethylene glycol) or a mixture of 50% cresylic acid and 50% ethylene glycol.
  • solvent media such as cresylic acid, n-methyl pyrrolidone, ethylene glycol, methyl Carbitol (monomethyl ether of diethylene glycol) or a mixture of 50% cresylic acid and 50% ethylene glycol.
  • polyester-imide resins of the invention are soluble in a wide variety of solvents including phenol, cresol or cresylic acid or other phenols or mixtures of phenols. They are preferably dissolved in a mixture of solvent containing 29-59% of cresylic Acid 43 (Merichem Co.), 12-19% of phenol, 17-38% of Solvesso 100 (a mixture of tetramethyl benzene with dialkyl- and trialkyl-benzene boiling in the range 182°-204° C.) or Solvesso 150 (a blend of 70% Solvesso 100 and 30% heavy aromatic naphtha).
  • solvents including phenol, cresol or cresylic acid or other phenols or mixtures of phenols. They are preferably dissolved in a mixture of solvent containing 29-59% of cresylic Acid 43 (Merichem Co.), 12-19% of phenol, 17-38% of Solvesso 100 (a mixture of tetramethyl benzene with dialkyl- and trial
  • the solvent can be a mixture of 0-60% water, 0-28% n-methyl pyrrolidone, 0-17% ethylene glycol and 12-89% methyl Carbitol.
  • various amines may be employed that react with the free carboxylic groups or amic acid groups available to form the salts that are soluble in water.
  • These amines may be of the alkyl and alkanolamines such as trimethylamine, triethylamine, triethanolamine, dimethylethanolamine, methyldiethanolamine.
  • a sufficient quantity of amine is employed to raise the pH of the aqueous solution to a range of 7-9 and preferably 7.5-8.5.
  • wire enamels of the invention there can be added to the wire enamels of the invention conventional modifiers such as Tyzor TPT (tetraisopropyltitanate), TBT (tetrabutyltitanate), tetraphenyltitanate, tetracresyltitanate, etc., as well as polyisocyanates, such as Mondur SH which is the cyclic trimer of 2,4 and 2,6-tolylene diisocyanates having the three free isocyanate groups blocked by phenol, or alternately any of the other polyisocyanates mentioned in Meyer U.S. Pat. No.
  • Tyzor TPT tetraisopropyltitanate
  • TBT tetrabutyltitanate
  • tetraphenyltitanate tetracresyltitanate
  • polyisocyanates such as Mondur SH which is the cyclic trimer of 2,4 and 2,6-tolylene diisocyanates having
  • cresol, or metal driers e.g., cobalt naphthenate, manganese naphthenate, calcium naphthenate, zinc octoate and Polycat 200.
  • titanate and driers e.g., any of those mentioned in Keating U.S. Pat. No. 4,119,608.
  • the wire enamels can be applied to copper, aluminum, silver or other wires using conventional coating procedures and wire speeds, e.g., 30-60 ft./min. and curing the wire is carried out at conventional temperatures, e.g., 260° C. to 482° C., usually 260°-427° C.
  • polyester-imide of the invention also has been found useful to provide a topcoat for wires base coated with a polyester resin or another polyester-imide resin to provide a coated wire having good heat shock properties.
  • the present polyester-imides provide this improved heat shock coated wires at lower cost than using a conventional amide-imide polymer top coat (the normal procedure is to apply 4 coats of polyester base coat (e.g., Isonel 200 prepared from tris(2-hydroxyethyl) isocyanurate, ethylene glycol and terephthalic acid) followed by 2 coats of the amide-imide polymer using N-methyl pyrrolidone as a solvent.
  • polyester base coat e.g., Isonel 200 prepared from tris(2-hydroxyethyl) isocyanurate, ethylene glycol and terephthalic acid
  • the polyester-imide enamel of the present invention as a topcoat (using 1 or 2 coats of the polyester-imide) for polyester (or a different polyester-imide) coated wire, there can be avoided the need for N-methyl pyrrolidone as a solvent. Lower cost solvents can be employed. Also, the enamel can be operated at higher solids content, e.g. 40%, so that less solvent goes up the stack.
  • the high temperature basecoats can be conventional polyesters, for example those set forth in Meyer U.S. Pat. No. 3,342,780 or convention polyester-imide resins, for example those in Meyer U.S. Pat. No. 3,426,098.
  • the entire disclosures of both Meyer patents is hereby incorporated by reference and relied upon.
  • Illustrative of the polyester resins are the reaction products of tris(2-hydroxyethyl) isocyanurate (THEIC), ethylene glycol and terephthalic acid or isophthalic acid.
  • TEEIC tris(2-hydroxyethyl) isocyanurate
  • ethylene glycol and terephthalic acid or isophthalic acid ethylene glycol
  • the THEIC in the base coat can be replaced by glycerine, trimethylolpropane or trimethylolethane.
  • polyester-imide resin base coat Illustrative of a polyester-imide resin base coat is the reaction product of THEIC, ethylene glycol, terephthalic acid (or isophthalic acid), methylene dianiline (or oxydianiline) and trimellitic anhydride.
  • THEIC there can be used glycerine, e.g. as in the polyester-imides of Schmidt U.S. Pat. No. 3,697,471, the entire disclosure of which is hereby incorporated by reference and relied upon.
  • the base coat there can be used as the base coat the diethylene glycol or triethylene glycol monoether modified polyester-imide resins of Keating U.S. Pat. No. 4,119,608, the entire disclosure of which is hereby incorporated by reference.
  • polyester-imide consists essentially of or consists of the stated materials.
  • composition can comprise, consist essentially of, or consist of the materials set forth.
  • TMA trimellitic anhydride
  • NMP N-methyl pyrrolidone
  • TPT tetraisopropyltitanate
  • DID diimide diacid (adduct of 1 mol of MDA and 2 moles of TMA)
  • Tyzor TE triethanolamine titanium chelate
  • ethylene glycol as the sole dihydric alcohol
  • another dihydric alcohol e.g., an alkanediol, such as 1,4-butylene glycol
  • an ethylene glycol-butylene glycol ratio of 75:25 there can be used an ethylene glycol-butylene glycol ratio of 75:25.
  • the imide content of the polyester-imide is expressed by
  • the polyester-imide was made with hydroxyl/carboxyl ratio of 3.33/1, triol/diol molar ratio of 0.45/1 and 50% imide content(equivalent).
  • Materials A, B, C, D and E were charged into a 3-liter, three-necked flask equipped with an agitator driven by an electronically-controlled motor, thermometer for flask, 3-bubble Snyder fractionating column and water-cooled condenser. The temperature was increased gradually to 220°-230° C. and held there until the desired physicals were attained.
  • X Gardner-Holdt
  • the solids of the resin were 86.7%, Molecular Weight of the polymer 987.
  • a solution of the polymer 1(a) was made by dissolving the resin in (B), (C) and (D) and holding the mixture at 120° C. with agitation until it was dissolved. The solution was cooled to 88° C. and (E), (F) and (G) were added. The solution was then heated to 120° C. and held for two hours. The viscosity of the resulting wire enamel was a V 3/4 and the solids were determined to be 39.2%.
  • the wire enamel was made by using the same procedure as described in Example 1(b) except the increased amounts of additives (F), (G) and (H) and 82.3 grams of Solvesso 150 were used in this formulation.
  • the viscosity of this enamel was an E and the solids were determined to be 28.4%.
  • the polyester-imide was made with imide content of 50 eq. % and a hydroxyl/carboxyl ratio of 3.67. The same procedure was used as described in Example 1(a). After a viscosity of U 1/2 was attained, the resin was discharged into a pan to solidify. The solids were determined to be 82.7%. The molecular weight of the polymer was 1082.
  • Polyester-imide 2(a) 386.8 grams, was used in place of 369.1 grams of polyester-imide 1(a) and the same procedure followed as in Example 1(b).
  • the viscosity of the resulting wire enamel was a U and the solids were determined to be 40.3%.
  • This polyester-imide with triol/diol molar ratio of 0.23/1 and imide content of 50 eq. % was made by using the same procedure as described in Example 1(a). A viscosity of U 1/2 and 79.6% solids were obtained for this polymer. The molecular weight of the polymer was 1290.
  • This polyester-imide with 47.5 equivalent % imide content was made by using the same procedure as described in Example 1(a).
  • This polymer had a viscosity of V and a solids of 86.0%.
  • the molecular weight was 1541.
  • the wire enamel solution was made by using the same procedure as described in Example 1(b) except with 371.7 grams of polyester-imide 4(a) in place of 369.1 grams of polyester-imide 1(a). This enamel had a viscosity of T 3/4 and a solids of 38.8%.
  • polyester-imide with 45 equivalent percent imide content was made by using the same procedure as outlined in Example 1(a) and the final polymer had a viscosity of V 1/4 and a solids of 85.5%.
  • the wire enamel was made by using the same procedure as described in Example 1(b). The viscosity of T 3/4 and solids of 39.4% were obtained for this wire enamel.
  • This polyester-imide with 45 equivalent % imide content and OH/COOH ratio of 2.65 was prepared by using the same equipment and procedure as outlined in Example 1(a). It was controlled to a final viscosity of X and a solids of 88.0%.
  • the wire enamel was made by using the same procedure as outlined in Example 1(b) except 363.3 grams of polyester-imide 6(a) were used in place of 369.1 grams of the polymer 1(a). A viscosity of V and a solids of 40.0% were obtained for this enamel.
  • This polyester-imide with 40 equivalent % imide content, OH/COOH ratio of 2.84 and triol/diol molar ratio of 0.29 was prepared by employing the same equipment and procedure as outlined in Example 1(a). It was controlled to a final viscosity of U 1/2 and solids of 82.6%. The molecular weight of the polymer was 773.
  • the wire enamel was made by using the same procedure as described in Example 1(b) except with 387 grams of polyester-imide 7(a) in place of 369.1 grams of polyester-imide 1(a). A viscosity of U 1/4 and solids of 40.0% were obtained for this enamel.
  • Example 1(a) The same equipment and procedure as outlined in Example 1(a) was employed in preparing this polymer except n-methyl pyrrolidone was used in place of cresylic acid as solvent medium. It was reacted to a viscosity of W at 38% solids in cresylic acid and a solids of 82.5%.
  • the wire enamel was made by using the same procedure as described in Example 1(b) except 364.5 grams of the polymer 8(a) was used in place of 369.1 grams of the polymer 1(a). A viscosity of X 1/2 and a solids of 40.3% were obtained for this wire enamel.
  • Example 1(a) The same equipment and procedure as outlined in Example 1(a) was employed in preparing this polymer except methyl Carbitol was used in place of cresylic acid as solvent medium. It was reacted to a viscosity of V 1/4 at 38% in cresylic acid and a solids of 80.9%.
  • the wire enamel was made by using the same procedure as described in Example 1(b) except 395.4 grams of the polymer 9(a) was used in place of 369.1 grams of the polymer 1(a). A viscosity of T 1/2 and a solids of 40.7% were obtained for this enamel.
  • Example 1(a) The same equipment and procedure as outlined in Example 1(a) was employed in preparing this polymer except ethylene glycol was used in place of cresylic acid as solvent medium. It was reacted to a viscosity of X 3/4 at 38% solids in cresylic acid and a solids of 88.7%.
  • the wire enamel was made by using the same procedure as described in Example 1(b) except 360.8 grams of the polymer 10(a) was used in place of 369.1 grams of the polymer 1(a). A viscosity of T and a solids of 41% were obtained for this enamel.
  • Example 5(a) This same equipment and procedure as outlined in Example 5(a) was employed in preparing this polymer except 61 grams of TA were replaced by 71.4 grams of DMT. It was controlled to a viscosity of U 1/4 at 38% in cresylic acid and a solids of 81.6%. The molecular weight of the polymer was 1481.
  • the wire enamel was made by using the same procedure as described in Example 1(b) except 391.8 grams of the polymer 11(a) were used in place of 369.1 grams of the polymer 1(a). A viscosity of U 1/2 and a solids of 40.5% were obtained for this enamel.
  • the wire enamel was made by using the same procedure as described in Example 1(b) except 377.4 grams of the polymer 12(a) were used in place of 369.1 grams of the polymer 1(a). A viscosity of U 3/4 and a solids of 39.2% were obtained for this enamel.
  • Example 1(a) The same equipment and procedure as outlined in Example 1(a) was employed in preparing this polymer except metal driers, (F), (G) and (H) were added. It was reacted to a viscosity of X 1/4 at 38% solids in cresylic acid and a solids of 86.1%.
  • the wire enamel was made by using the same procedure as described in Example 1(b) except 371.7 grams of polymer 13(a) were used to replace 369.1 grams of polymer 1(a). A viscosity of V 1/2 and a solids of 41.4% were obtained for this enamel.
  • Example 1(a) The same equipment and procedure as outlined in Example 1(a) was employed in preparing this polymer except 342.5 grams of excess ethylene glycol was used in this formulation. It was controlled to a final viscosity of U 3/4 and a solids of 82.6%.
  • the wire enamel was prepared by using the same procedure as described in Example 1(b) except 387.4 grams of the polymer 14(a) was used to replace 369.1 grams of the polymer 1(a). A viscosity of U and a solids of 41.6% were obtained for this enamel.
  • the percent solids of the base polymer and wire enamel solutions were determined using two-gram samples in a forced-air oven held at 200° C. for two hours.
  • the heat shock was tested at 260° C. for one-half hour at 20% prestretch and the results reported as the percent passed.
  • CA-43 a product of Merichem Co., is a mixture of phenol and its alkyl derivatives which has the following composition:
  • polyester-imides of the present invention as indicated above are usefu as a top coat for wires having a base coat of a polyester or of a different polyester-imide.
  • the polyester-imide products of the present invention produce electrical conductor coatings having extraordinarily high heat resistance.
  • Thermobonding and high heat resistance are mutually exclusive properties.
  • a polymer having a structure that will lend the polymer softenable and bondable at temperatures such as 175° C. will not be able to withstand the performance rigors that the present polyester-imide product withstands at 260° C.
  • the present product that is constructed to withstand 260° C. does not show the following bondability at 175° C.
  • the present high, heat resistance polymer has absolutely no bond strength and therefore undergoes no softening at conditions used by the Keske to obtain bonding for their polymers.
  • the Keske and Czajka polyester-imide coatings are high molecular weight thermoplastic compositions while the polyester-imide coatings of the present invention are low molecular weight thermosetting resins generally having an acid value between 0 and 10.
  • the basecoat was Isonel 200 (tris-2-hydroxyethyl) isocyanurate-ethylene glycolterephthalate).
  • the wire construction contained four coats of the basecoat and two coats of the respective topcoats, except for the last sample of the new E.I. where there was only one topcoat layer and five Isonel 200 basecoat layers.
  • the topcoat referred to as AI is a polyamide-imide based on the following formulation:
  • the enamel solution was prepared in a conventional manner similar to that used in the other examples to give an enamel having a solids content of 26.5-28.5% and a viscosity of T 1/2-U 1/2 on the Gardner-Holdt scale.
  • the topcoat referred to as "New EI” is the product described in Example 1 of the patent application.
  • AI/ISONEL construction is based on a polyamideimide at approximately 22-28% solids using very expensive N-methyl-pyrrolidone as a solvent.
  • the new polyesterimide uses conventional cresylic acid/hydrocarbon solvent blends which are considerably cheaper, and employs considerably higher solids levels.

Abstract

A low molecular weight polyester-imide resin is prepared wherein there is employed as the dibasic acid either 100% of the diimide dicarboxylic prepared by reacting two moles of trimellitic anhydride with one mole of methylene dianiline (the diimide is abbreviated DID) or oxydianiline or the dibasic acid can also contain a small percent of another aromatic acid. The product is used to produce coated wires having outstanding heat shock. The product also is useful to provide a top coat to wire coated with a polyester or with another polyester-imide.

Description

REFERENCE TO THE RELATED APPLICATION
This application is a continuation-in-part of application Ser. No. 220,160, filed Dec. 23, 1980 and now abandoned.
BACKGROUND OF THE INVENTION
The present invention relates to the preparation of novel polyester-imides and their use in coating wires with outstanding physical properties.
In Schmidt U.S. Pat. No. 3,697,471, there is disclosed in Example 9 a polyester-imide prepared from ethylene glycol, glycerine and a diimide dicarboxylic acid prepared by reacting two moles of trimellitic anhydride with one mole of methylene dianiline. This diimide dicarboxylic acid is sometimes abbreviated hereinafter as DID. The polymers prepared in Schmidt have a triol to diol molar ratio of 0.676, a hydroxy to carboxy equivalent ratio of 1.41. The product has a 250° C. heat shock without using prestretch of the wire and employing one hour of baking.
The commercial material made under the Schmidt patent known as Terebec FH contains substantial amounts of ester derived from terephthalic acid and a small amount of imide derived from DID. Terebec FH in inferior in properties to the commercial polyester-imide, ISOMID, made in accordance with Meyer U.S. Pat. No. 3,426,098. Thus, in regard to heat shock precent passing one-half hour at 200° C. using 20 percent prestretch, the following results are noted.
______________________________________                                    
Mandrel Size   Terebec FH ISOMID                                          
______________________________________                                    
1X             30          0                                              
2X             50          80                                             
3X             60         100                                             
4X             90         100                                             
______________________________________
When ISOMID was tested at 260° C., the results in the same Mandrel Sizes was 0-0-0-0.
It has previously been proposed to use polyesterimide resins as a top coat for electrical conductors coated with a polyester resin or other resin, e.g., Ishizuka U.S. Pat. No. 4,208,464, Keske U.S. Pat. No. 4,070,524, Czajka U.S. Pat. No. 3,944,706, Keske U.S. Pat. No. 4,012,555, and Keske U.S. Pat. No. 4,012,556. However, the products of these patents do not have sufficiently good heat shock properties. In fact, a number of these patents, e.g., the Keske and Czajka patents, are directed to self-bonding coatings for magnet wires. The self-bonding property is incompatible with good heat shock properties. Ishizuka prepares a water soluble polyester-imide having an acid value of 30-50, an OH/COOH equivalent ratio of 1:1 to 2:1 and requires a substantial amount of an aliphatic polycarboxylic acid.
SUMMARY OF THE INVENTION
It has now been found that there can be prepared a polyester-imide having outstanding physical properties when applied to a wire. Thus, it is capable of withstanding heat shock at 260° C. compared to the 200° C. of the commercial ISOMID referred to above. The new polyester-imide can compete, as a single-coat system, against the amide-imide topcoated polyester (e.g., amide-imide coated ISONEL 200/ system now used in the art). The new polyester-imide passes the A. O. Smith blister test and had good burn-out results.
The new polyester-imide employs as the dicarboxylic acid DID or a mixture of DID with a small amount of another aromatic dicarboxylic acid.
The parameters of the invention are as follows:
(1) A polyester-imide is made with a hydroxyl to carboxyl equivalent ratio of 2.65:1 to 3.67:1, preferably 2.65:1 to 3.33:1. The ratio can even be as high as 4.0:1.
(2) A polyester-imide is made with trihydric alcohol to dihydric alcohol molar ratio of 0.23:1 to 0.62:1, preferably 0.4:1 to 0.5:1.
(3) The polyester-imide is made with 40-50%, usually 42.5-50%, by equivalent, imide groups, preferably 45-50%, by equivalent, imide groups.
(4) The polyester-imide is made with the following mole percentages of ingredients:
______________________________________                                    
                  Mole %                                                  
______________________________________                                    
Dihydric alcohol    29-56                                                 
Trihydric alcohol    9-19                                                 
Aromatic Diamine    11-18                                                 
Trimellitic Anhydride                                                     
                    22-35                                                 
Aromatic Diacid or Diester                                                
                     0-7                                                  
______________________________________
It should be noted that the molar ratios of the reactants change quite considerably depending on whether one starts with trimellitic anhydride and methylene dianiline on the one hand or prereacts them and then bases the calculation on the preformed DID. Two moles of TMA and one mole of MDA are condensed to become only one mole of DID, thereby changing the molar calculation. In Example 12 for instance, the mole percent of THEIC is 23% based on the use of DID, or 15.3% when the MDA and TMA are not prereacted to form DID. THEIC molar percentages are always higher in those cases using prereacted DID, because the DID always involve a fewer number of total moles and therefore the contribution of the THEIC becomes proportionately greater.
The mole ratios in parameter (4) and in the claims are calculated on a basis that TMA and the diamine are present rather than preformed DID.
(5) The polyester-imide normally has an average molecular weight of from 700 to 1300 or even up to 2,000, but preferably an average molecular weight of from 750-1050. The molecular weights were determined by Vapor Pressure Osmometer.
(6) The hydroxyl number of the polyester-imide frequently is within 380-420, but this can be varied, e.g., it can be as low as 350 or as high as 450.
(7) The polyester-imide is made using (1) tris (2-hydroxyethyl) isocyanurate (THEIC), (2) a dibasic acid such as terephthalic acid (TA) or its lower alkyl esters, e.g., dimethyl terephthalate (DMT), diethyl terephthalate or dibutyl terephthalate, (3) trimellitic anhydride (TMA), (4) a diamine, such as methylene dianiline or oxydianiline, preferably methylene dianiline and (5) a dihydric alcohol such as ethylene glycol.
(8) The polyester-imides of this invention can be cooked at 70-100% concentration in various kinds of solvent media, such as cresylic acid, n-methyl pyrrolidone, ethylene glycol, methyl Carbitol (monomethyl ether of diethylene glycol) or a mixture of 50% cresylic acid and 50% ethylene glycol.
(9) The polyester-imide resins of the invention are soluble in a wide variety of solvents including phenol, cresol or cresylic acid or other phenols or mixtures of phenols. They are preferably dissolved in a mixture of solvent containing 29-59% of cresylic Acid 43 (Merichem Co.), 12-19% of phenol, 17-38% of Solvesso 100 (a mixture of tetramethyl benzene with dialkyl- and trialkyl-benzene boiling in the range 182°-204° C.) or Solvesso 150 (a blend of 70% Solvesso 100 and 30% heavy aromatic naphtha). The solvent can be a mixture of 0-60% water, 0-28% n-methyl pyrrolidone, 0-17% ethylene glycol and 12-89% methyl Carbitol. To solubilize these polyester-imides in water, various amines may be employed that react with the free carboxylic groups or amic acid groups available to form the salts that are soluble in water. These amines may be of the alkyl and alkanolamines such as trimethylamine, triethylamine, triethanolamine, dimethylethanolamine, methyldiethanolamine. A sufficient quantity of amine is employed to raise the pH of the aqueous solution to a range of 7-9 and preferably 7.5-8.5.
There can be added to the wire enamels of the invention conventional modifiers such as Tyzor TPT (tetraisopropyltitanate), TBT (tetrabutyltitanate), tetraphenyltitanate, tetracresyltitanate, etc., as well as polyisocyanates, such as Mondur SH which is the cyclic trimer of 2,4 and 2,6-tolylene diisocyanates having the three free isocyanate groups blocked by phenol, or alternately any of the other polyisocyanates mentioned in Meyer U.S. Pat. No. 3,426,098, or cresol, or metal driers, e.g., cobalt naphthenate, manganese naphthenate, calcium naphthenate, zinc octoate and Polycat 200. There can be used other titanate and driers, e.g., any of those mentioned in Keating U.S. Pat. No. 4,119,608. Also there can be added to the enamel phenolic resins such as phenol-formaldehyde cresol-formaldehyde resins.
The wire enamels can be applied to copper, aluminum, silver or other wires using conventional coating procedures and wire speeds, e.g., 30-60 ft./min. and curing the wire is carried out at conventional temperatures, e.g., 260° C. to 482° C., usually 260°-427° C.
The polyester-imide of the invention also has been found useful to provide a topcoat for wires base coated with a polyester resin or another polyester-imide resin to provide a coated wire having good heat shock properties. Moreover, the present polyester-imides provide this improved heat shock coated wires at lower cost than using a conventional amide-imide polymer top coat (the normal procedure is to apply 4 coats of polyester base coat (e.g., Isonel 200 prepared from tris(2-hydroxyethyl) isocyanurate, ethylene glycol and terephthalic acid) followed by 2 coats of the amide-imide polymer using N-methyl pyrrolidone as a solvent.
Instead of using the amide-imide polymer when there is employed the polyester-imide enamel of the present invention as a topcoat (using 1 or 2 coats of the polyester-imide) for polyester (or a different polyester-imide) coated wire, there can be avoided the need for N-methyl pyrrolidone as a solvent. Lower cost solvents can be employed. Also, the enamel can be operated at higher solids content, e.g. 40%, so that less solvent goes up the stack.
The high temperature basecoats can be conventional polyesters, for example those set forth in Meyer U.S. Pat. No. 3,342,780 or convention polyester-imide resins, for example those in Meyer U.S. Pat. No. 3,426,098. The entire disclosures of both Meyer patents is hereby incorporated by reference and relied upon. Illustrative of the polyester resins are the reaction products of tris(2-hydroxyethyl) isocyanurate (THEIC), ethylene glycol and terephthalic acid or isophthalic acid. For Class F enamels, the THEIC in the base coat can be replaced by glycerine, trimethylolpropane or trimethylolethane.
Illustrative of a polyester-imide resin base coat is the reaction product of THEIC, ethylene glycol, terephthalic acid (or isophthalic acid), methylene dianiline (or oxydianiline) and trimellitic anhydride. In place of THEIC, there can be used glycerine, e.g. as in the polyester-imides of Schmidt U.S. Pat. No. 3,697,471, the entire disclosure of which is hereby incorporated by reference and relied upon. Likewise, there can be used as the base coat the diethylene glycol or triethylene glycol monoether modified polyester-imide resins of Keating U.S. Pat. No. 4,119,608, the entire disclosure of which is hereby incorporated by reference.
The polyester-imide consists essentially of or consists of the stated materials.
The composition can comprise, consist essentially of, or consist of the materials set forth.
Unless otherwise indicated, all parts and percentages are by weight.
The following abbreviations are used in the examples:
EG=ethylene glycol
TA=terephthalic acid
DMT=dimethyl terephthalate
TMA=trimellitic anhydride
THEIC=tris-(2-hydroxyethyl) isocyanurate
MDA=methylene dianiline
NMP=N-methyl pyrrolidone
TPT=tetraisopropyltitanate
DID=diimide diacid (adduct of 1 mol of MDA and 2 moles of TMA)
Tyzor TE=triethanolamine titanium chelate
It has been found critical to use the stated materials. Thus, replacing THEIC by trimethylol propane or glycerine does not give as good results nor does replacing terephthalic acid by isophthalic acid or adipic acid as the other acid when less than 100% DID is used as the acid component. Likewise, replacing ethylene glycol with propylene glycol or 1,4-butanediol does not give as good results nor does including 1,2,3,4-butane tetracarboxylic anhydride as part of the acid. While it is preferable to employ ethylene glycol as the sole dihydric alcohol, it is possible to replace a minor portion of the ethylene glycol by another dihydric alcohol, e.g., an alkanediol, such as 1,4-butylene glycol. For example, there can be used an ethylene glycol-butylene glycol ratio of 75:25.
The imide content of the polyester-imide is expressed by
EXAMPLE 1 (a) Preparation of Polymer 
______________________________________                                    
             Weight            Mol % of                                   
Reactants    Grams      Mols   Total Reactants                            
______________________________________                                    
(A)     CA-43    321.9      --   --                                       
(B)     EG       230.7      3.72 33.7                                     
(C)     THEIC    440.8      1.69 15.3                                     
(D)     TMA      721.0      3.76 34.0                                     
(E)     MDA      371.9      1.88 17.0                                     
______________________________________
The polyester-imide was made with hydroxyl/carboxyl ratio of 3.33/1, triol/diol molar ratio of 0.45/1 and 50% imide content(equivalent). Materials A, B, C, D and E were charged into a 3-liter, three-necked flask equipped with an agitator driven by an electronically-controlled motor, thermometer for flask, 3-bubble Snyder fractionating column and water-cooled condenser. The temperature was increased gradually to 220°-230° C. and held there until the desired physicals were attained. At a viscosity of X (Gardner-Holdt) as measured at 38% solids in cresylic acid the reaction was terminated, and the melt discharged into a pan to solidify. The solids of the resin were 86.7%, Molecular Weight of the polymer 987.
(b) Preparation of Wire Enamel 
______________________________________                                    
                          Weight,                                         
                          Grams                                           
______________________________________                                    
(A)  The polyester-imide prepared                                         
                                369.1                                     
     in Example (1a)                                                      
(B)  CA-43                      120.7                                     
(C)  Phenol                     90.5                                      
(D)  Solvesso 100               172.4                                     
(E)  Phenolic Resin (m, p Cresol-formaldehyde                             
                                36.6                                      
     resin-% by weight dissolved in                                       
     CA-43)                                                               
(F)  TPT                        12.2                                      
(G)  Blocked Isocyanate (Mondur SH-% by weight                            
                                70.4                                      
     dissolved in CA-43 and Solvesso 100)                                 
(H)  Ethylene Glycol            17.0                                      
______________________________________
A solution of the polymer 1(a) was made by dissolving the resin in (B), (C) and (D) and holding the mixture at 120° C. with agitation until it was dissolved. The solution was cooled to 88° C. and (E), (F) and (G) were added. The solution was then heated to 120° C. and held for two hours. The viscosity of the resulting wire enamel was a V 3/4 and the solids were determined to be 39.2%.
(c) Preparation of Wire Enamel 
______________________________________                                    
                   Weight, Grams                                          
______________________________________                                    
(A)     The polyester-imide                                               
                         262.4                                            
        prepared in Example 1(a)                                          
(B)     CA-43            247.0                                            
(C)     Phenol           109.8                                            
(D)     Solvesso 150     82.3                                             
(E)     Solvesso 100     109.8                                            
(F)     Phenolic Resin   29.6                                             
(G)     TPT              10.0                                             
(H)     Blocked Isocyanate                                                
                         63.1                                             
______________________________________
The wire enamel was made by using the same procedure as described in Example 1(b) except the increased amounts of additives (F), (G) and (H) and 82.3 grams of Solvesso 150 were used in this formulation. The viscosity of this enamel was an E and the solids were determined to be 28.4%.
(d) Preparation of Wire Enamel 
______________________________________                                    
                   Weight, Grams                                          
______________________________________                                    
(A)     The polyester-imide                                               
                         262.4                                            
        prepared in Example 1(a)                                          
(B)     CA-43            238.8                                            
(C)     Phenol           106.1                                            
(D)     Solvesso 150     79.6                                             
(E)     Solvesso 100     106.1                                            
(F)     Phenolic Resin   17.4                                             
(G)     TPT              6.4                                              
(H)     Blocked Isocyanate                                                
                         40.3                                             
______________________________________
The wire enamel was made by using the same procedure as described in Example 1(b). The viscosity of this enamel was a D 3/4 and the solids were determined to be 28.3%.
EXAMPLE 2 (a) Preparation of Polymer 
______________________________________                                    
             Weight,           Mol % of                                   
Reactants    Grams      Mols   Total Reactants                            
______________________________________                                    
(A)     CA-43    330.2      --   --                                       
(B)     EG       232.5      3.75 35.4                                     
(C)     THEIC    440.6      1.69 16.0                                     
(D)     TMA      657.6      3.43 32.4                                     
(E)     MDA      339.1      1.71 16.2                                     
______________________________________
The polyester-imide was made with imide content of 50 eq. % and a hydroxyl/carboxyl ratio of 3.67. The same procedure was used as described in Example 1(a). After a viscosity of U 1/2 was attained, the resin was discharged into a pan to solidify. The solids were determined to be 82.7%. The molecular weight of the polymer was 1082.
(b) Preparation of Wire Enamel
Polyester-imide 2(a), 386.8 grams, was used in place of 369.1 grams of polyester-imide 1(a) and the same procedure followed as in Example 1(b). The viscosity of the resulting wire enamel was a U and the solids were determined to be 40.3%.
EXAMPLE 3 (a) Preparation of Polymer 
______________________________________                                    
             Weight,           Mol % of                                   
Reactants    Grams      Mols   Total Reactants                            
______________________________________                                    
(A)     CA-43    358.7      --   --                                       
(B)     EG       319.7      5.16 41.0                                     
(C)     THEIC    309.3      1.19  9.4                                     
(D)     TMA      799.8      4.17 33.1                                     
(E)     MDA      412.4      2.08 16.5                                     
______________________________________
This polyester-imide with triol/diol molar ratio of 0.23/1 and imide content of 50 eq. % was made by using the same procedure as described in Example 1(a). A viscosity of U 1/2 and 79.6% solids were obtained for this polymer. The molecular weight of the polymer was 1290.
(b) Preparation of Wire Enamel
Polyester-imide 3(a), 401.6 grams, was used in place of 369.1 grams of polyester-imide 1(a) and the same procedure followed as in Example 1(b). The viscosity of the resulting wire enamel was a U 1/2 and the solids were determined to be 40.2%.
EXAMPLE 4 (a) Preparation of Polymer 
______________________________________                                    
             Weight,           Mol % of                                   
Reactants    Grams      Mols   Total Reactants                            
______________________________________                                    
(A)     CA-43    394.8      --   --                                       
(B)     EG       286.0      4.61 34.9                                     
(C)     THEIC    542.1      2.08 15.7                                     
(D)     TMA      806.4      4.20 31.8                                     
(E)     MDA      415.8      2.10 15.9                                     
(F)     TA        36.5      0.22  1.7                                     
______________________________________
This polyester-imide with 47.5 equivalent % imide content was made by using the same procedure as described in Example 1(a). This polymer had a viscosity of V and a solids of 86.0%. The molecular weight was 1541.
(b) Preparation of Wire Enamel
The wire enamel solution was made by using the same procedure as described in Example 1(b) except with 371.7 grams of polyester-imide 4(a) in place of 369.1 grams of polyester-imide 1(a). This enamel had a viscosity of T 3/4 and a solids of 38.8%.
EXAMPLE 5 (a) Preparation of Polymer 
______________________________________                                    
             Weight,           Mol % of                                   
Reactants    Grams      Mols   Total Reactants                            
______________________________________                                    
(A)     CA-43    321.9      --   --                                       
(B)     EG       251.7      4.06 36.0                                     
(C)     THEIC    475.1      1.82 16.2                                     
(D)     TMA      641.3      3.34 29.7                                     
(E)     MDA      330.7      1.67 14.8                                     
(F)     TA        61.0      0.37  3.3                                     
______________________________________
This polyester-imide with 45 equivalent percent imide content was made by using the same procedure as outlined in Example 1(a) and the final polymer had a viscosity of V 1/4 and a solids of 85.5%.
(b) Preparation of Wire Enamel
The wire enamel was made by using the same procedure as described in Example 1(b). The viscosity of T 3/4 and solids of 39.4% were obtained for this wire enamel.
EXAMPLE 6 (a) Preparation of Polymer 
______________________________________                                    
             Weight,           Mol % of                                   
Reactants    Grams      Mols   Total Reactants                            
______________________________________                                    
(A)     CA-43    347.9      --   --                                       
(B)     EG       278.9      4.50 32.1                                     
(C)     THEIC    529.1      2.03 14.5                                     
(D)     TMA      894.7      4.66 33.2                                     
(E)     MDA      461.3      2.33 16.6                                     
(F)     TA        85.0      0.51  3.6                                     
______________________________________
This polyester-imide with 45 equivalent % imide content and OH/COOH ratio of 2.65 was prepared by using the same equipment and procedure as outlined in Example 1(a). It was controlled to a final viscosity of X and a solids of 88.0%.
(b) Preparation of Wire Enamel
The wire enamel was made by using the same procedure as outlined in Example 1(b) except 363.3 grams of polyester-imide 6(a) were used in place of 369.1 grams of the polymer 1(a). A viscosity of V and a solids of 40.0% were obtained for this enamel.
EXAMPLE 7 (a) Preparation of Polymer 
______________________________________                                    
            Weight             Mol % of                                   
Reactants   Grams      Mols    Total Reactants                            
______________________________________                                    
(A)    CA-43    149.3      --    --                                       
(B)    EG       184.8      2.98  40.6                                     
(C)    THEIC    222.4      0.852 11.6                                     
(D)    TMA      384.0      2.0   27.3                                     
(E)    MDA      198.0      1.0   13.6                                     
(F)    TA        83.0      0.5    6.8                                     
______________________________________
This polyester-imide with 40 equivalent % imide content, OH/COOH ratio of 2.84 and triol/diol molar ratio of 0.29 was prepared by employing the same equipment and procedure as outlined in Example 1(a). It was controlled to a final viscosity of U 1/2 and solids of 82.6%. The molecular weight of the polymer was 773.
(b) Preparation of Wire Enamel
The wire enamel was made by using the same procedure as described in Example 1(b) except with 387 grams of polyester-imide 7(a) in place of 369.1 grams of polyester-imide 1(a). A viscosity of U 1/4 and solids of 40.0% were obtained for this enamel.
EXAMPLE 8 (a) Preparation of Polymer
The same equipment and procedure as outlined in Example 1(a) was employed in preparing this polymer except n-methyl pyrrolidone was used in place of cresylic acid as solvent medium. It was reacted to a viscosity of W at 38% solids in cresylic acid and a solids of 82.5%.
(b) Preparation of Conventional Wire Enamel
The wire enamel was made by using the same procedure as described in Example 1(b) except 364.5 grams of the polymer 8(a) was used in place of 369.1 grams of the polymer 1(a). A viscosity of X 1/2 and a solids of 40.3% were obtained for this wire enamel.
(c) Preparation of Aqueous Wire Enamels
The hard resin 8(a) was then fractured into small chunks, and 472.7 grams of the polymer along with 39.1 grams of methyl Carbitol was charged to a 3-liter, three-necked round-bottom flask, and heated to 132° C. until the polymer was fluid and dissolved. At a temperature of 120° C., 46.8 grams of dimethylethanolamine (DMEA) was added to the flask. Then the batch was cooled to 105° C., 182.1 grams of distilled water was added to the flask. Additional water, amine and solvent were added to reduce the viscosity. Then on a solids-to-solids basis 5.5% Tyzor TE was added to the solution to make the final enamel having a viscosity of X 1/4, a pH of 8 and a solids of 47.6%.
EXAMPLE 9 (a) Preparation of Polymer
The same equipment and procedure as outlined in Example 1(a) was employed in preparing this polymer except methyl Carbitol was used in place of cresylic acid as solvent medium. It was reacted to a viscosity of V 1/4 at 38% in cresylic acid and a solids of 80.9%.
(b) Preparation of Conventional Wire Enamel
The wire enamel was made by using the same procedure as described in Example 1(b) except 395.4 grams of the polymer 9(a) was used in place of 369.1 grams of the polymer 1(a). A viscosity of T 1/2 and a solids of 40.7% were obtained for this enamel.
(c) Preparation of Aqueous Wire Enamel
Using the same equipment and procedure as described in 8(c) an aqueous enamel was prepared by blending 481.9 grams of base polymer 9(a) with 29.9 grams of methyl Carbitol, 66.8 grams of DMEA, 182.6 grams of distilled water and 21.9 grams of Tyzor TE to provide an enamel having the following properties: viscosity=X 1/2, pH=7.5, % solids=53.0%.
EXAMPLE 10 (a) Preparation of Polymer 
______________________________________                                    
             Weight,           Mol % of                                   
Reactants    Grams      Mols   Total Reactants                            
______________________________________                                    
(A)     EG       552.6      8.91 54.9                                     
(B)     THEIC    440.8      1.69 10.4                                     
(C)     TMA      721.0      3.76 23.2                                     
(D)     MDA      371.9      1.88 11.6                                     
______________________________________
The same equipment and procedure as outlined in Example 1(a) was employed in preparing this polymer except ethylene glycol was used in place of cresylic acid as solvent medium. It was reacted to a viscosity of X 3/4 at 38% solids in cresylic acid and a solids of 88.7%.
(b) Preparation of Conventional Wire Enamel
The wire enamel was made by using the same procedure as described in Example 1(b) except 360.8 grams of the polymer 10(a) was used in place of 369.1 grams of the polymer 1(a). A viscosity of T and a solids of 41% were obtained for this enamel.
(c) Preparation of Aqueous Wire Enamel
Using the same equipment and procedure as described in 8(c) an aqueous enamel was prepared by blending 439.7 grams of polymer 10(a), 72.1 grams of methyl Carbitol, 66.8 grams of DMEA, 182.6 grams of distilled water and 21.9 grams of Tyzor TE to provide an enamel having the following properties: viscosity=Y, pH=7.5, and % solids=48.6%.
EXAMPLE 11 (a) Preparation of Polymer 
______________________________________                                    
            Weight,            Mol % of                                   
Reactants   Grams      Mols    Total Reactants                            
______________________________________                                    
(A)    CA-43    318.4      --    --                                       
(B)    EG       249.0      4.02  36.1                                     
(C)    THEIC    471.8      1.81  16.2                                     
(D)    TMA      634.5      3.30  29.6                                     
(E)    MDA      327.3      1.65  14.8                                     
(F)    DMT       71.4       0.368                                         
                                  3.3                                     
(G)    Xylol                                                              
______________________________________
This same equipment and procedure as outlined in Example 5(a) was employed in preparing this polymer except 61 grams of TA were replaced by 71.4 grams of DMT. It was controlled to a viscosity of U 1/4 at 38% in cresylic acid and a solids of 81.6%. The molecular weight of the polymer was 1481.
(b) Preparation of Wire Enamel
The wire enamel was made by using the same procedure as described in Example 1(b) except 391.8 grams of the polymer 11(a) were used in place of 369.1 grams of the polymer 1(a). A viscosity of U 1/2 and a solids of 40.5% were obtained for this enamel.
EXAMPLE 12 (a) Preparation of Polymer 
______________________________________                                    
             Weight,           Mol % of                                   
Reactants    Grams      Mols   Total Reactants                            
______________________________________                                    
(A)     CA-43    63.8       --   --                                       
(B)     EG       45.7       0.737                                         
                                 51.1                                     
(C)     THEIC    87.3       0.334                                         
                                 23.1                                     
(D)     DID      203.2      0.372                                         
                                 25.8                                     
______________________________________
The same equipment and procedure as outlined in Example 1(a) was employed in preparing this polymer except DID was used in place of TMA and MDA. It was reacted to a viscosity of U 3/4 at 38% in cresylic acid and a solids of 84.8%. The molecular weight of the polymer was 1967.
(b) Preparation of Wire Enamel
The wire enamel was made by using the same procedure as described in Example 1(b) except 377.4 grams of the polymer 12(a) were used in place of 369.1 grams of the polymer 1(a). A viscosity of U 3/4 and a solids of 39.2% were obtained for this enamel.
EXAMPLE 13 (a) Preparation of Polymer 
______________________________________                                    
               Weight,         Mol % of                                   
Reactants      Grams    Mols   Total Reactants                            
______________________________________                                    
(A)    CA-43       321.9    --   --                                       
(B)    EG          230.7    3.72 33.7                                     
(C)    THEIC       440.8    1.69 15.3                                     
(D)    TMA         721.0    3.76 34.0                                     
(E)    MDA         371.9    1.88 17.0                                     
(F)    Cobalt      24 ppm*                                                
       Naphthenate                                                        
(G)    Calcium     96 ppm*                                                
       Naphthenate                                                        
(H)    Manganese   72 ppm*                                                
       Naphthenate                                                        
______________________________________                                    
 *Based on total solids of the batch
The same equipment and procedure as outlined in Example 1(a) was employed in preparing this polymer except metal driers, (F), (G) and (H) were added. It was reacted to a viscosity of X 1/4 at 38% solids in cresylic acid and a solids of 86.1%.
(b) Preparation of Wire Enamel
The wire enamel was made by using the same procedure as described in Example 1(b) except 371.7 grams of polymer 13(a) were used to replace 369.1 grams of polymer 1(a). A viscosity of V 1/2 and a solids of 41.4% were obtained for this enamel.
EXAMPLE 14 (a) Preparation of Polymer 
______________________________________                                    
             Weight,           Mol % of                                   
Reactants    Grams      Mols   Total Reactants                            
______________________________________                                    
(A)     CA-43    321.9      --   --                                       
(B)     EG       573.2      9.25 55.8                                     
(C)     THEIC    440.8      1.69 10.2                                     
(D)     TMA      721.0      3.76 22.7                                     
(E)     MDA      371.9      1.88 11.3                                     
______________________________________
The same equipment and procedure as outlined in Example 1(a) was employed in preparing this polymer except 342.5 grams of excess ethylene glycol was used in this formulation. It was controlled to a final viscosity of U 3/4 and a solids of 82.6%.
(b) Preparation of Wire Enamel
The wire enamel was prepared by using the same procedure as described in Example 1(b) except 387.4 grams of the polymer 14(a) was used to replace 369.1 grams of the polymer 1(a). A viscosity of U and a solids of 41.6% were obtained for this enamel.
The percent solids of the base polymer and wire enamel solutions were determined using two-gram samples in a forced-air oven held at 200° C. for two hours.
After applying the enamels to the wire at room temperature, they were baked on in a conventional manner at 260°-480° C.
The heat shock was tested at 260° C. for one-half hour at 20% prestretch and the results reported as the percent passed.
The following table shows the properties with 18-gauge copper wire coated with the compositions of some of the examples described above.
                                  TABLE 1                                 
__________________________________________________________________________
Wire                                         Dissipa-                     
Speed         Mandrel                                                     
                   Cut                                                    
                      260° C.                                      
                                    Burn     tion                         
Ft/           After                                                       
                   Thru                                                   
                      Heat Shock                                          
                              Unidirect.                                  
                                    Out Freon                             
                                             Factor                       
                                                  Build                   
Example                                                                   
     Min.                                                                 
         Appear                                                           
              Snap °C.                                             
                      1X                                                  
                        2X                                                
                          3X                                              
                            4X                                            
                              Scrape                                      
                                    (sec.)                                
                                        Resist.                           
                                             (240° C.)             
                                                  (mils)                  
__________________________________________________________________________
1(b) 45  3    2X   370                                                    
                      80-90-100-100                                       
                              1000-1410                                   
                                    465      2.34 2.8                     
1(b) 50  3    1X   355                                                    
                      60-90-100-100                                       
                              1100-1116                                   
                                    417 OK-OK                             
                                             3.29 2.8                     
1(b) 55  3    1X   340                                                    
                      90-100-100-100                                      
                              1100-1416                                   
                                    410      3.89 2.8                     
1(b) 60  3    1X   280                                                    
                      80-100-100-100                                      
                              1166-1283                                   
                                    427      3.49 2.9                     
1(c) 50  4    1X   355                                                    
                      70-80-100-100               3.0                     
1(d) 50  4    1X   360                                                    
                      80-100-100-100              3.0                     
2(b) 50  3    1X   355                                                    
                      60-70-90-100                                        
                              1250-1400           2.8                     
3(b) 50  3    1X   325                                                    
                      70-90-100-100               2.9                     
4(b) 50  3    1X   375                                                    
                      70-80-100-100               2.9                     
5(b) 45  3    1X   370                                                    
                      30-80-100-100                                       
                              1000- 1000          2.9                     
6(b) 50  3    1X   360                                                    
                      40-80-100-100                                       
                              1200-1416           3.0                     
7(b) 50  3    1X   360                                                    
                      50-80-90-100                                        
                              1000-1500           3.0                     
8(b) 50  4    1X   320                                                    
                      10-80-90-100                3.0                     
8(c) 50  3    1X   295                                                    
                      50-80-100-100                                       
                              1300-1466           2.9                     
9(b) 50  4    1X   350                                                    
                      50-90-100-100                                       
                              1000-1250           2.9                     
9(c) 50  4    1X   290                                                    
                      10-80-100-100                                       
                              1000-1216           2.9                     
10(b)                                                                     
     45  3    1X   365                                                    
                      10-70-90-100                                        
                              1100-1450                                   
                                    475      3.62 3.0                     
13(b)                                                                     
     45  3    1X   385                                                    
                      30-90-100-100                                       
                              1450-1450                                   
                                    459      3.51 2.9                     
14(b)                                                                     
     50  4    1X   355                                                    
                      50-80-90-100                                        
__________________________________________________________________________
A. O. Smith Freon Test
This is a standard Freon test developed by A. O. Smith Co.
Procedure
Prepare a coil using 5 feet of coated wire. Wind the coil on a mandrel (A. O. Smith specifications) to produce a 4-6% stretch on the wire. For 18 gauge, this is a mandrel of 1-1/6 inch outer diameter. Prebake coiled samples for two hours at 150° C. Remove and cool samples. Place in the Freon bomb and charge with 11/2 pounds Freon 22. Raise the bomb pressure by heating to 600 psi and hold for six hours. Release pressure and immediately place coils in an oven at 150° C. for four hours. Remove coils and check for blistering. The samples fail according to the following: one large blister (in excess of wire diameter), two medium blisters (from one-half to one wire diameter) or five small blisters (less than half the wire diameter). A flexibility test is also run by wrapping a length of wire on a 5X mandrel for 10 turns. The film should not crack or peel. In addition, a twisted pair dielectric is run on the samples that pass the previous tests.
The Composition of CA-43
CA-43, a product of Merichem Co., is a mixture of phenol and its alkyl derivatives which has the following composition:
______________________________________                                    
Component         % by Weight                                             
______________________________________                                    
Phenol            6-8                                                     
O-cresol           9-10                                                   
M-cresol          15-20                                                   
P-cresol           8-11                                                   
O-Ethylphenol     1-3                                                     
M-Ethylphenol      9-11                                                   
P-Ethylphenol     3-5                                                     
2,6-Dimethylphenol                                                        
                  1                                                       
2,4-Dimethylphenol                                                        
                  11-17                                                   
2,5-Dimethylphenol                                                        
2,3-Dimethylphenol                                                        
                  10-13                                                   
3,5-Dimethylphenol                                                        
3,4-Dimethylphenol                                                        
                  5-8                                                     
2,4,6-Trimethylphenol                                                     
                  1                                                       
______________________________________                                    
 The formula of DID is                                                    
 ##STR1##
The polyester-imides of the present invention as indicated above are usefu as a top coat for wires having a base coat of a polyester or of a different polyester-imide. The polyester-imide products of the present invention produce electrical conductor coatings having extraordinarily high heat resistance.
Thermobonding and high heat resistance are mutually exclusive properties. A polymer having a structure that will lend the polymer softenable and bondable at temperatures such as 175° C. will not be able to withstand the performance rigors that the present polyester-imide product withstands at 260° C. Likewise, the present product that is constructed to withstand 260° C. does not show the following bondability at 175° C. Experiments show that the present high, heat resistance polymer has absolutely no bond strength and therefore undergoes no softening at conditions used by the Keske to obtain bonding for their polymers.
Moreover, the Keske and Czajka polyester-imide coatings are high molecular weight thermoplastic compositions while the polyester-imide coatings of the present invention are low molecular weight thermosetting resins generally having an acid value between 0 and 10.
In following Table 2, the basecoat was Isonel 200 (tris-2-hydroxyethyl) isocyanurate-ethylene glycolterephthalate). The wire construction contained four coats of the basecoat and two coats of the respective topcoats, except for the last sample of the new E.I. where there was only one topcoat layer and five Isonel 200 basecoat layers.
In Table 2 the topcoat referred to as AI is a polyamide-imide based on the following formulation:
______________________________________                                    
N--methylpyrrolidone                                                      
                 (NMP)   80.4      grams                                  
Methylene diphenyl       25.0      grams                                  
diisocyanate     (MDI)                                                    
Amyl alcohol             0.85      grams                                  
Trimellitic anhydride                                                     
                 (TMA)   19.1      grams                                  
Solvesso 100             34.3      grams                                  
______________________________________
These ingredients were cooked in conventional manner to produce an enamel solution having a viscosity range of X 1/2-Y on the Gardner-Holdt scale at a solids content of 26.5-28.5% based on a two-gram sample that is baked for two hours in a forced air oven at 200° C. The topcoat referred to as ISOMID is based on the following formulation:
______________________________________                                    
Polyesterimide resin at 82.5% solids                                      
                         115.2   grams                                    
Cresylic Acid            177.4   grams                                    
Solvesso 100             112.8   grams                                    
Cresol formaldehyde resin at 40 ± 2% solids                            
                         15.1    grams                                    
Tetra Isopropyl Titanate 5.1     grams                                    
Isocyanate resin at 40 ± 2% solids, Mondur SH                          
                         32.8    grams                                    
840 Silicone Resin       0.35    grams                                    
______________________________________
The enamel solution was prepared in a conventional manner similar to that used in the other examples to give an enamel having a solids content of 26.5-28.5% and a viscosity of T 1/2-U 1/2 on the Gardner-Holdt scale.
The topcoat referred to as "New EI" is the product described in Example 1 of the patent application.
                                  TABLE 2                                 
__________________________________________________________________________
AL/ISONEL® ISOMID®/ISONEL®                                    
                           New E.I./ISONEL®                           
__________________________________________________________________________
Pass  2/4      2/4         2/4    1/5                                     
Heat Shock                                                                
260° C.                                                            
      80-80-90-100                                                        
               0-0-0-0     10-50-70-80                                    
                                  10-20-40-60                             
220° C.                                                            
      80-100-100-100                                                      
               0-0-0-0     30-40-70-100                                   
                                  70-80-90-100                            
200° C.                                                            
      80-100-100-100                                                      
               60-80-90-100                                               
                           80-100-100-100                                 
                                  50-80-90-100                            
Windability                                                               
      Pass 24  Pass 20     Pass 24                                        
                                  Pass 13                                 
(1500V)                                                                   
A.O.Smith                                                                 
(Freon)                                                                   
Blister                                                                   
      Two large blisters                                                  
               Fails       Few Blisters                                   
                                  Fails                                   
      Top coat lossened                                                   
Flex  Passes   Fails       Passes Fails                                   
Diel(KV)                                                                  
      16.5     Fails       14.0   Fails                                   
After                                                                     
__________________________________________________________________________
If there is compared the heat shock values at 200° C., it can be seen that all constructions are approximately equal in performance. However, as the temperature of heat shocking is raised to 220° C., the construction with the ISOMID topcoat completely fails the test. The new polyesterimide covered passes a 4X mandrel at 220° C. At 220° and 260° C., it does not quite measure up exactly to the heat shock resistance of the AI/ISONEL construction, but offers acceptable performance at a much lower price. AI/ISONEL construction is based on a polyamideimide at approximately 22-28% solids using very expensive N-methyl-pyrrolidone as a solvent. The new polyesterimide uses conventional cresylic acid/hydrocarbon solvent blends which are considerably cheaper, and employs considerably higher solids levels.
In order to show the difference between the new polyester-imide topcoat and that of the Keske patent, ISONEL 200 coated wire was topcoated with the new polyester-imide and the coated wire was wound, bonded at 175° C. for 1 hour and tested for bond strength. The results compared to that of Keske are set forth below.
______________________________________                                    
Bond Strength, lbs. at                                                    
Sample     RT     175° C.                                          
______________________________________                                    
New E.I.   0      0                                                       
(of Example 1)                                                            
Keske's E.I.                                                              
           14.5   1.5       (U.S. Pat. No. 4,012,255,                     
                            col. 8, line 49)                              
______________________________________

Claims (77)

What is claimed is:
1. A polyester-imide having a hydroxy to carboxy equivalent ratio of 2.65:1 to 3.67:1, a trihydric alcohol to dihydric alcohol molar ratio of 0.23:1 to 0.62:1, the polyester-imide containing 40 to 50 equivalent % of imide groups, the imide groups being from the imide dibasic acid of the formula ##STR2## the polyester having been made with the following mole percentages of ingredients:
______________________________________                                    
                      Mol %                                               
______________________________________                                    
dihydric alcohol        29-56                                             
trihydric alcohol        9-19                                             
aromatic diamine        11-18                                             
trimellitic anhydride   22-35                                             
aromatic diacid or diester                                                
                         0-7                                              
______________________________________
wherein the dihydric alcohol is ethylene glycol, the trihydric alcohol is tris(2-hydroxyethyl) isocyanurate, the aromatic diamine is methylene dianiline, the mole ratio of trimellitic anhydride to methylene dianiline is about 2:1, the aromatic diacid is terephthalic acid and the aromatic diester is a di(lower alkyl) terephthalate, the polyester-imide has a molecular weight of 700 to 2000, the hydroxyl number of the polyester-imide is 350 to 450, said polyester-imide being capable of forming a single coat insulating coating on an electrical wire capable of withstanding heat shock at 260° C.
2. A polyester-imide according to claim 1 wherein there is employed terephthalic acid.
3. A polyester-imide according to claim 1 wherein the aromatic diacid or diester content is 0.
4. A polyester-imide according to claim 1 wherein the aromatic diacid or diester content is 2-7 mole %.
5. A polyester-imide according to claim 1 having a molecular weight of 750-1050.
6. A polyester-imide according to claim 1 having a hydroxy to carboxyl equivalent ratio of 2.65:1 to 3.33:1, a trihydric alcohol to dihydric alcohol molar ratio of 0.4:1 to 0.5:1 and the polyester-imide contains 42.5-50 equivalent % of imide groups.
7. A polyester-imide according to claim 6 wherein the polyester-imide contains 45-50 equivalent % of imide groups.
8. A process of preparing the polyesterimide of claim 1 comprising heating (1) the dihydric alcohol, trihydric alcohol, aromatic diamine and trimellitic anhydride or (2) the dihydric alcohol, trihydric alcohol, aromatic diamine, trimellitic anhydride and the aromatic diacid or diester in an organic solvent until the polyester-imide is formed.
9. A process of preparing the polyesterimide of claim 1 comprising heating (1) the dihydric alcohol, trihydric alcohol or (2) the dihydric alcohol, trihydric alcohol, performed imide dibasic acid and aromatic diacid or diester in an organic solvent until the polyester-imide is formed.
10. An electrical conductor having an insulating coating prepared by curing the polyesterimide of claim 1 thereon.
11. An electrical conductor according to claim 10 wherein the conductor is in the form of wire.
12. An electrical conductor in wire form having an insulating coating prepared by curing the polyester-imide of claim 2 thereon.
13. An electrical conductor in wire form having an insulating coating prepared by curing the polyester-imide of claim 3 thereon.
14. An electrical conductor in wire form having an insulating coating prepared by curing the polyester-imide of claim 4 thereon.
15. An electrical conductor in wire form having an insulating coating prepared by curing the polyester-imide of claim 5 thereon.
16. An electrical conductor in wire form having an insulating coating prepared by curing the polyester-imide of claim 6 thereon.
17. An electrical conductor in wire form having an insulating coating prepared by curing the polyester-imide of claim 7 thereon.
18. A coating composition containing the polyester-imide of claim 1 dissolved in an organic solvent.
19. A coating composition according to claim 18 free from water.
20. A coating composition comprising an aqueous solvent and the reaction product of the polyester-imide of claim 1 with sufficient amount of a tertiary amine to render the reaction product soluble in the aqueous solvent mixture.
21. A coating composition according to claim 20 having a pH of 7 to 9.
22. A coating composition according to claim 21 wherein the pH is 7.5 to 8.5.
23. A process of preparing an insulated electrical conductor wire comprising applying to the wire the coating composition of claim 21 and curing the polyester-imide on the wire.
24. The insulated wire produced by the process of claim 23.
25. The process of preparing an insulated electrical conductor wire comprising applying to the wire the coating composition of claim 20 and curing the polyester-imide on the wire.
26. The insulated wire prepared by the process of claim 25.
27. The process of preparing an insulated electrical conductor wire comprising applying to the wire the coating composition of claim 19 and curing the polyester-imide on the wire.
28. The insulated wire prepared by the process of claim 27.
29. The polyester-imide according to claim 1 having a molecular weight of 700-1300.
30. A polyester-imide having a hydroxy to carboxy equivalent ratio of 2.65:1 to 4.0:1, a trihydric alcohol to dihydric alcohol molar ratio of 0.23:1 to 0.62:1, the polyester-imide containing 40 to 50 equivalent % of imide groups, the imide groups being from the imide dibasic acid of the formula ##STR3## where X is O or CH2, the polyester having been made with the following mole percentages of ingredients:
______________________________________                                    
                      Mol %                                               
______________________________________                                    
dihydric alcohol        29-56                                             
trihydric alcohol        9-19                                             
aromatic diamine        11-18                                             
trimellitic anhydride   22-35                                             
aromatic diacid or diester                                                
                         0-7                                              
______________________________________
wherein the dihydric alcohol is ethylene glycol or a mixture of ethylene glycol and a minor amount of another alkanediol, the trihydric alcohol is tris(2-hydroxyethyl) isocyanurate, the aromatic diamine is methylene dianiline or oxydianiline, the mole ratio of trimellitic anhydride to methylene dianiline or oxydianiline is about 2:1, the aromatic diacid is terephthalic acid and the aromatic diester is a di(lower alkyl) terephthalate, the polyester-imide has a molecular weight of 700 to 2000, the hydroxyl number of the polyester-imide is 350 to 450, said polyester-imide being capable of forming a single coat insulating coating on an electrical wire capable of withstanding heat shock at 260° C.
31. A polyester-imide according to claim 30 wherein the aromatic diamine is oxydianiline and the hydroxy to carboxy equivalent ratio is 2.65:1 to 3.67:1.
32. An electrical conductor having an insulating top coat prepared by curing the polyester-imide of claim 30 thereon and a base coat of a polyester or a different polyester-imide.
33. An electrical conductor according to claim 32 wherein the base coat is a polyester.
34. An electrical conductor according to claim 33 wherein the polyester is a tris(2-hydroxyethyl) isocyanurateethylene glycol terephthalate polymer.
35. An electrical conductor according to claim 33 wherein the conductor is in the form of a wire.
36. An electrical conductor according to claim 32 wherein the conductor is in the form of a wire.
37. An electrical conductor having an insulating top coat prepared by curing the polyester-imide of claim 1 thereon and a base coat of a polyester or a different polyester-imide.
38. An electrical conductor according to claim 37 wherein the base coat is a polyester.
39. An electrical conductor according to claim 38 wherein the polyester is a tris(2-hydroxyethyl) isocyanurateethylene glycol terephthalate polymer.
40. An electrical conductor according to claim 38 wherein the conductor is in the form of a wire.
41. An electrical conductor according to claim 37 wherein the conductor is in the form of a wire.
42. An electrical conductor according to claim 41 wherein there is employed terephthalic acid as a component of the polyester-imide having an equivalent ratio of 2.65:1 to 3.67:1.
43. An electrical conductor according to claim 41 wherein said aromatic diacid or diester content is 0.
44. An electrical conductor according to claim 41 wherein said aromatic diacid or diester content is 2-7 mole %.
45. An electrical conductor according to claim 41 wherein the molecular weight of the polyester-imide having an equivalent ratio of 2.65:1 to 3.67:1 is 750-1050.
46. An electrical conductor according to claim 41 wherein the polyester-imide has a hydroxy to carboxyl equivalent ratio of 2.65:1 to 3.33:1, a trihydric alcohol to dihydric alcohol molar ratio of 0.4:1 to 0.5:1 and the polyester-imide contains 42.5-50 equivalent % of imide groups.
47. An electrical conductor according to claim 46 wherein the polyester-imide contains 45-50 equivalent % of imide groups.
48. A process of preparing an insulated electrical conductor wire comprising applying to the wire a base coat of a polyester or a polyester-imide and there applying a top coat of the polyester-imide of claim 30, the polyester-imide of the base coat being different from that of the top coat.
49. A process of preparing an insulated electrical conductor wire comprising applying to the wire a base coat of a polyester or a polyester-imide and there applying a top coat of the polyester-imide of claim 1, the polyester-imide of the base coat being different from that of the top coat.
50. An electrical conductor according to claim 10 wherein the coating also contains a phenol-formaldehyde or cresol-formaldehyde resin.
51. An electrical conductor according to claim 50 wherein the coating contains a m,p-cresol-formaldehyde resin.
52. A coating composition according to claim 18 including a phenol-formaldehyde or cresol-formaldehyde resin.
53. A coating composition according to claim 32 including a m,p-cresol-formaldehyde resin.
54. A coating composition according to claim 20 including a phenol-formaldehyde or cresol-formaldehyde resin.
55. A coating composition according to claim 54 including a m,p-cresol-formaldehyde resin.
56. A process according to claim 25 wherein the coating composition includes a phenol-formaldehyde or cresol-formaldehyde resin.
57. The insulated wire produced by the process of claim 56.
58. A process according to claim 56 wherein the coating composition includes a m,p-cresol-formaldehyde resin.
59. The insulated wire produced by the process of claim 58.
60. A process according to claim 27 wherein the coating composition includes a phenol-formaldehyde or cresol-formaldehyde resin.
61. The insulated wire produced by the process of claim 60.
62. In an electrical conductor having an insulating coating comprising a polyesterimide the improvement of employing as the polyesterimide the product obtained by curing the polyesterimide of claim 1 on said electrical conductor.
63. In a coating composition containing a polyester-imide dissolved in an organic solvent the improvement comprising employing as the polyester-imide the polyester-imide of claim 1.
64. In a coating composition comprising an aqueous solvent and a polyester-imide the improvement comprising employing as the polyester-imide the reaction product of the polyester-imide of claim 1 with sufficient amount of a tertiary amine to render the reaction product soluble in the aqueous solvent mixture.
65. An electrical conductor according to claim 32 wherein the coating also contains a phenol-formaldehyde or cresol-formaldehyde resin.
66. An electrical conductor according to claim 65 wherein the coating contains a m,p-cresol-formaldehyde resin.
67. An electrical conductor according to claim 33 wherein the top coat also contains a phenol-formaldehyde or cresol-formaldehyde resin.
68. An electrical conductor according to claim 34 wherein the top coat also contains a phenol-formaldehyde or cresol-formaldehyde resin.
69. A process according to claim 48 wherein the top coating composition includes a phenol-formaldehyde or cresol-formaldehyde resin.
70. The insulated wire produced by the process of claim 69.
71. A process according to claim 69 wherein the coating composition includes a m,p-cresol-formaldehyde resin.
72. The insulated wire produced by the process of claim 71.
73. A process according to claim 49 wherein the coating composition includes a phenol-formaldehyde or cresol-formaldehyde resin.
74. The insulated wire produced by the process of claim 73.
75. In an electrical conductor having an insulating coating comprising a polyesterimide the improvement of employing as the polyesterimide the product obtained by curing the polyesterimide of claim 30 on said electrical conductor.
76. In a coating composition containing a polyester-imide dissolved in an organic solvent the improvement comprising employing as the polyester-imide the polyester-imide of claim 30.
77. In a coating composition comprising an aqueous solvent and a polyester-imide the improvement comprising employing as the polyester-imide the reaction product of the polyester-imide of claim 30 with sufficient amount of a tertiary amine to render the reaction product soluble in the aqueous solvent mixture.
US06/311,386 1980-12-23 1981-10-14 Polyesterimide Expired - Fee Related US4362861A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US06/311,386 US4362861A (en) 1980-12-23 1981-10-14 Polyesterimide
CA000392277A CA1180488A (en) 1980-12-23 1981-12-15 Polyesterimide
AR28783181A AR227453A1 (en) 1980-12-23 1981-12-16 POLYESTERIMIDE AND PROCEDURE TO PREPARE IT
AU78609/81A AU543192B2 (en) 1980-12-23 1981-12-17 Polyesterimide
EP19810305928 EP0055085A1 (en) 1980-12-23 1981-12-17 Polyester imides and coating compositions and electrically insulated coatings formed from them
BR8108351A BR8108351A (en) 1980-12-23 1981-12-22 POLYESTER-IMIDA, PROCESS FOR ITS PREPARATION, ELECTRICAL CONDUCTOR, COMPOSITION OF COATING, PROCESS FOR THE PREPARATION OF AN INSULATED ELECTRIC CONDUCTING WIRE THE INSULATED WIRE
JP17363188A JPS6426679A (en) 1980-12-23 1988-07-12 Coating composition
JP17363088A JPS6426678A (en) 1980-12-23 1988-07-12 Conductor and its production

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US22016080A 1980-12-23 1980-12-23
US06/311,386 US4362861A (en) 1980-12-23 1981-10-14 Polyesterimide

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US22016080A Continuation-In-Part 1980-12-23 1980-12-23

Publications (1)

Publication Number Publication Date
US4362861A true US4362861A (en) 1982-12-07

Family

ID=26914618

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/311,386 Expired - Fee Related US4362861A (en) 1980-12-23 1981-10-14 Polyesterimide

Country Status (7)

Country Link
US (1) US4362861A (en)
EP (1) EP0055085A1 (en)
JP (2) JPS6426678A (en)
AR (1) AR227453A1 (en)
AU (1) AU543192B2 (en)
BR (1) BR8108351A (en)
CA (1) CA1180488A (en)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4544734A (en) * 1984-10-26 1985-10-01 General Electric Company Modified thermoplastic copolyetherimide ester elastomers
US4552950A (en) * 1985-01-11 1985-11-12 General Electric Company Polyetherimide esters
US4556688A (en) * 1984-10-26 1985-12-03 General Electric Company Thermoplastic polyetherimide ester elastomers
US4556705A (en) * 1984-10-26 1985-12-03 General Electric Company Thermoplastic polyetherimide ester elastomers
US4594377A (en) * 1984-10-26 1986-06-10 General Electric Company Modified thermoplastic copolyetherimide ester elastomers
US4598117A (en) * 1985-01-11 1986-07-01 General Electric Company Elastomeric compositions comprising a combination of (a) an aromatic thermoplastic polyester and (b) clay/syenite
US4605710A (en) * 1985-04-05 1986-08-12 Minnesota Mining And Manufacturing Company High temperature wire coating powder
US4740564A (en) * 1986-12-02 1988-04-26 General Electric Company Thermoplastic polyetherimide esters
US4921761A (en) * 1987-05-08 1990-05-01 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Polyester imide resins
US4997891A (en) * 1986-09-08 1991-03-05 Schenectady Chemicals, Inc. High temperature resistant fast soldering wire enamel
US5322920A (en) * 1990-07-25 1994-06-21 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Thermosetting esterimide oligomer and its production method
US5580950A (en) * 1993-04-21 1996-12-03 The University Of Akron Negative birefringent rigid rod polymer films
US6461730B1 (en) * 1991-09-20 2002-10-08 Danfoss A/S Lubricant for wire used for forming the stator windings of an electrical refrigerating compressor
US20100136333A1 (en) * 2007-04-27 2010-06-03 Valspar Sourcing, Inc. Crosslinkable imide polyester coating
US20120048592A1 (en) * 2010-08-25 2012-03-01 Hitachi Cable, Ltd Polyester imide resin insulating coating material, insulated wire using same, and coil
US20130153262A1 (en) * 2010-08-24 2013-06-20 Sumitomo Electric Industries, Ltd. Polyester imide resin based varnish for low-permittivity coating film
US9109079B2 (en) 2009-02-20 2015-08-18 Elantas Gmbh Eco-friendly solderable wire enamel
EP3093320A1 (en) 2011-11-04 2016-11-16 Valspar Sourcing, Inc. Coating composition for packaging articles
EP2935487B1 (en) 2012-12-18 2019-06-19 PPG Industries Ohio, Inc. A coating composition

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4769475A (en) * 1985-03-19 1988-09-06 Nippon Telegraph And Telephone Corporation Bis(hydroxyphthalimide) and process for preparing the same, and process for preparing polyesterimide by the use thereof
DE3542857A1 (en) * 1985-12-04 1987-06-11 Basf Ag FULLY AROMATIC MESOMORPHE POLYESTERIMIDES
JPS63152625A (en) * 1986-07-07 1988-06-25 Idemitsu Kosan Co Ltd Novel polyester and production thereof
EP0666336B1 (en) 1993-07-27 2001-10-17 Kabushiki Kaisha Toshiba Method for producing a high melting point metallic silicide target
DE19648830A1 (en) 1996-11-26 1998-05-28 Beck & Co Ag Dr Process for the preparation of carboxyl- and hydroxyl-containing polyester imides and their use in wire enamels
DE102008004926A1 (en) * 2008-01-18 2009-07-23 Elantas Gmbh High temperature resistant electrical insulating varnish
JP5876686B2 (en) * 2011-08-10 2016-03-02 住友電工ウインテック株式会社 Insulating material
CN104673085B (en) * 2015-03-09 2017-07-28 溧阳市佳禾电子材料有限公司 A kind of heat resistant type enamelled wire insulated paint and preparation method thereof

Citations (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3312573A (en) * 1963-05-06 1967-04-04 Schenectady Chemical Non-linear overcoat for coated electrical conductor
US3342780A (en) * 1961-06-16 1967-09-19 Schenectady Chemical Reaction product of a dibasic polycarboxylic acid and tris (2-hydroxyethyl) isocyanurate
US3426098A (en) * 1965-05-20 1969-02-04 Schenectady Chemical Polyester-polyimide wire enamel
US3697471A (en) * 1961-11-02 1972-10-10 Beck & Co Ag Dr Polyester imide resin lacquers
US3817926A (en) * 1970-12-14 1974-06-18 Gen Electric Polyamide-imides
US3833546A (en) * 1972-12-29 1974-09-03 Gen Electric Method for making polyetherimides
US3853817A (en) * 1971-06-17 1974-12-10 Gen Electric Tin containing esterimide polymer resins and method of forming
US3922252A (en) * 1972-06-23 1975-11-25 Gen Electric Polyamideimide compositions
US3944706A (en) * 1974-08-01 1976-03-16 Standard Oil Company Self-bonding polyethylene trimellitate imide varnish
US3959233A (en) * 1973-04-09 1976-05-25 Standard Oil Company (Indiana) Process for preparing polyamide-imide from trimellitic acid, diamine and diisocyanate and polyamide imide shaped articles
US3975330A (en) * 1974-05-01 1976-08-17 Nitto Electric Industrial Co., Ltd. Imide-modified polyester resin and wire enamel containing the imide-modified polyester resin
US3988283A (en) * 1975-04-03 1976-10-26 Rea Magnet Wire Co., Inc. Wire enamel with low soldering temperature
US4012555A (en) * 1976-02-23 1977-03-15 Standard Oil Company (Indiana) Self-bonding varnish for magnet wires comprising a combination of a polyalkylenetrimellitate imide and a polyalkylenetrimellitate ester imide
US4012556A (en) * 1976-02-23 1977-03-15 Standard Oil Company (Indiana) Self-bonding varnish for magnet wires comprising a polyalkylenetrimellitate ester imide
US4018736A (en) * 1974-12-20 1977-04-19 Badische Anilin- & Soda-Fabrik Aktiengesellschaft Manufacture of polyester-imide powders
US4066593A (en) * 1975-10-23 1978-01-03 Standard Oil Company (Indiana) Water soluble wire enamels
US4070524A (en) * 1976-02-23 1978-01-24 Standard Oil Company (Indiana) Self-bonding varnish for magnetic wire comprising polyalkylenetrimellitate imide polyalkylenetrimellitate ester
US4075179A (en) * 1975-12-24 1978-02-21 Essex International, Inc. Polyesterimides and processes for preparing same
US4081427A (en) * 1974-12-20 1978-03-28 The P. D. George Company Solventless electrical insulation resins
US4101488A (en) * 1974-09-26 1978-07-18 Nitto Electric Industrial Co., Ltd. Water-soluble heat-resistant insulating varnish
US4105639A (en) * 1977-05-11 1978-08-08 Schenectady Chemicals, Inc. Water soluble polyester resin
US4117032A (en) * 1976-09-23 1978-09-26 Westinghouse Electric Corp. Wire coating powder
US4116941A (en) * 1976-06-01 1978-09-26 Standard Oil Company, A Corporation Of Indiana Water-soluble polyester-imides
US4119608A (en) * 1977-02-22 1978-10-10 Schenectady Chemicals, Inc. Solutions of polyester-imides
US4127553A (en) * 1976-04-20 1978-11-28 Hitachi Chemical Company, Ltd. Electrical insulating resin composition comprising a polyester resin or ester-imide resin
US4145334A (en) * 1961-11-02 1979-03-20 Dr. Beck & Co., A.G. Polyester imide resins
US4208464A (en) * 1974-09-26 1980-06-17 Nitto Electric Industrial Co., Ltd. Article coated with baked layer of water-soluble heat-resistant insulating varnish

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4038254A (en) * 1973-03-01 1977-07-26 Dynamit Nobel Aktiengesellschaft Process for the manufacture of wire insulation varnish resins suitable chiefly for application in the melted state
DE2522386C3 (en) * 1975-05-21 1984-09-27 Chemische Fabrik Dr.Wiedeking, 4152 Kempen Electrical insulating varnish
US4179423A (en) * 1976-06-09 1979-12-18 Schenectady Chemicals, Inc. Water-soluble polyester imide resins
US4104221A (en) * 1976-08-24 1978-08-01 Dr. Beck & Co., Ag Process for making water diluted electroinsulation enamels

Patent Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3342780A (en) * 1961-06-16 1967-09-19 Schenectady Chemical Reaction product of a dibasic polycarboxylic acid and tris (2-hydroxyethyl) isocyanurate
US3697471A (en) * 1961-11-02 1972-10-10 Beck & Co Ag Dr Polyester imide resin lacquers
US4145334A (en) * 1961-11-02 1979-03-20 Dr. Beck & Co., A.G. Polyester imide resins
US3312573A (en) * 1963-05-06 1967-04-04 Schenectady Chemical Non-linear overcoat for coated electrical conductor
US3426098A (en) * 1965-05-20 1969-02-04 Schenectady Chemical Polyester-polyimide wire enamel
US3817926A (en) * 1970-12-14 1974-06-18 Gen Electric Polyamide-imides
US3853817A (en) * 1971-06-17 1974-12-10 Gen Electric Tin containing esterimide polymer resins and method of forming
US3922252A (en) * 1972-06-23 1975-11-25 Gen Electric Polyamideimide compositions
US3833546A (en) * 1972-12-29 1974-09-03 Gen Electric Method for making polyetherimides
US3959233A (en) * 1973-04-09 1976-05-25 Standard Oil Company (Indiana) Process for preparing polyamide-imide from trimellitic acid, diamine and diisocyanate and polyamide imide shaped articles
US3975330A (en) * 1974-05-01 1976-08-17 Nitto Electric Industrial Co., Ltd. Imide-modified polyester resin and wire enamel containing the imide-modified polyester resin
US3944706A (en) * 1974-08-01 1976-03-16 Standard Oil Company Self-bonding polyethylene trimellitate imide varnish
US4208464A (en) * 1974-09-26 1980-06-17 Nitto Electric Industrial Co., Ltd. Article coated with baked layer of water-soluble heat-resistant insulating varnish
US4101488A (en) * 1974-09-26 1978-07-18 Nitto Electric Industrial Co., Ltd. Water-soluble heat-resistant insulating varnish
US4018736A (en) * 1974-12-20 1977-04-19 Badische Anilin- & Soda-Fabrik Aktiengesellschaft Manufacture of polyester-imide powders
US4081427A (en) * 1974-12-20 1978-03-28 The P. D. George Company Solventless electrical insulation resins
US4115342A (en) * 1975-04-03 1978-09-19 Rea Magnet Wire Co., Inc. Wire enamel with low soldering temperature
US3988283A (en) * 1975-04-03 1976-10-26 Rea Magnet Wire Co., Inc. Wire enamel with low soldering temperature
US4066593A (en) * 1975-10-23 1978-01-03 Standard Oil Company (Indiana) Water soluble wire enamels
US4075179A (en) * 1975-12-24 1978-02-21 Essex International, Inc. Polyesterimides and processes for preparing same
US4070524A (en) * 1976-02-23 1978-01-24 Standard Oil Company (Indiana) Self-bonding varnish for magnetic wire comprising polyalkylenetrimellitate imide polyalkylenetrimellitate ester
US4012556A (en) * 1976-02-23 1977-03-15 Standard Oil Company (Indiana) Self-bonding varnish for magnet wires comprising a polyalkylenetrimellitate ester imide
US4012555A (en) * 1976-02-23 1977-03-15 Standard Oil Company (Indiana) Self-bonding varnish for magnet wires comprising a combination of a polyalkylenetrimellitate imide and a polyalkylenetrimellitate ester imide
US4127553A (en) * 1976-04-20 1978-11-28 Hitachi Chemical Company, Ltd. Electrical insulating resin composition comprising a polyester resin or ester-imide resin
US4116941A (en) * 1976-06-01 1978-09-26 Standard Oil Company, A Corporation Of Indiana Water-soluble polyester-imides
US4117032A (en) * 1976-09-23 1978-09-26 Westinghouse Electric Corp. Wire coating powder
US4119608A (en) * 1977-02-22 1978-10-10 Schenectady Chemicals, Inc. Solutions of polyester-imides
US4105639A (en) * 1977-05-11 1978-08-08 Schenectady Chemicals, Inc. Water soluble polyester resin

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4544734A (en) * 1984-10-26 1985-10-01 General Electric Company Modified thermoplastic copolyetherimide ester elastomers
US4556688A (en) * 1984-10-26 1985-12-03 General Electric Company Thermoplastic polyetherimide ester elastomers
US4556705A (en) * 1984-10-26 1985-12-03 General Electric Company Thermoplastic polyetherimide ester elastomers
US4594377A (en) * 1984-10-26 1986-06-10 General Electric Company Modified thermoplastic copolyetherimide ester elastomers
US4552950A (en) * 1985-01-11 1985-11-12 General Electric Company Polyetherimide esters
US4598117A (en) * 1985-01-11 1986-07-01 General Electric Company Elastomeric compositions comprising a combination of (a) an aromatic thermoplastic polyester and (b) clay/syenite
US4605710A (en) * 1985-04-05 1986-08-12 Minnesota Mining And Manufacturing Company High temperature wire coating powder
US4997891A (en) * 1986-09-08 1991-03-05 Schenectady Chemicals, Inc. High temperature resistant fast soldering wire enamel
US4740564A (en) * 1986-12-02 1988-04-26 General Electric Company Thermoplastic polyetherimide esters
US4921761A (en) * 1987-05-08 1990-05-01 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Polyester imide resins
US5322920A (en) * 1990-07-25 1994-06-21 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Thermosetting esterimide oligomer and its production method
US5391697A (en) * 1990-07-25 1995-02-21 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Method of producing a thermosetting esterimide oligomer
US6461730B1 (en) * 1991-09-20 2002-10-08 Danfoss A/S Lubricant for wire used for forming the stator windings of an electrical refrigerating compressor
US6562767B1 (en) * 1991-09-30 2003-05-13 Danfoss Compressors Gmbh Process for producing a lubricant coated laquered wire used for forming the stator winding of an electrical refrigerating compressor
US5580950A (en) * 1993-04-21 1996-12-03 The University Of Akron Negative birefringent rigid rod polymer films
US20100136333A1 (en) * 2007-04-27 2010-06-03 Valspar Sourcing, Inc. Crosslinkable imide polyester coating
US8758888B2 (en) 2007-04-27 2014-06-24 Valspar Sourcing, Inc. Crosslinkable imide polyester coating
US9109079B2 (en) 2009-02-20 2015-08-18 Elantas Gmbh Eco-friendly solderable wire enamel
US20130153262A1 (en) * 2010-08-24 2013-06-20 Sumitomo Electric Industries, Ltd. Polyester imide resin based varnish for low-permittivity coating film
US20120048592A1 (en) * 2010-08-25 2012-03-01 Hitachi Cable, Ltd Polyester imide resin insulating coating material, insulated wire using same, and coil
CN102385948A (en) * 2010-08-25 2012-03-21 日立卷线株式会社 Polyester imide resin insulating coating material, insulated wire using same, and coil
US8986834B2 (en) * 2010-08-25 2015-03-24 Hitachi Metals, Ltd. Polyester imide resin insulating coating material, insulated wire using same, and coil
CN102385948B (en) * 2010-08-25 2015-08-19 日立金属株式会社 The insulated electric conductor of polyesterimide resin coatings and this coating of use and coil
EP3093320A1 (en) 2011-11-04 2016-11-16 Valspar Sourcing, Inc. Coating composition for packaging articles
EP2935487B1 (en) 2012-12-18 2019-06-19 PPG Industries Ohio, Inc. A coating composition

Also Published As

Publication number Publication date
EP0055085A1 (en) 1982-06-30
JPH0126622B2 (en) 1989-05-24
JPH0126623B2 (en) 1989-05-24
JPS6426678A (en) 1989-01-27
JPS6426679A (en) 1989-01-27
BR8108351A (en) 1982-10-13
AU7860981A (en) 1982-07-01
AR227453A1 (en) 1982-10-29
AU543192B2 (en) 1985-04-04
CA1180488A (en) 1985-01-02

Similar Documents

Publication Publication Date Title
US4362861A (en) Polyesterimide
US3555113A (en) Blends of polymeric amide-imide-ester wire enamels and conductors insulated therewith
US3652471A (en) Polyester amide-imide wire enamels
US4431758A (en) Heat resistant resin composition comprising reaction product of polyamideimide resin, alcohol and acid component.
JP5842458B2 (en) Polyesterimide resin insulating paint, insulated wire using the same, and coil
US4496715A (en) Amide-imide-ester wire enamels
US3960799A (en) Heat-resistant adhesive lacquers as wire coatings
US4075179A (en) Polyesterimides and processes for preparing same
US4180612A (en) Hydantoin-polyester coating compositions
US3201276A (en) Insulated conductor having undercoat of isocyanurate modified polyester and overcoat of polyethylene terephthalate
US3406045A (en) Cross-linked polyethylene terephthalate overcoat for insulated electrical conductors
US4477624A (en) Heat-resistant synthetic resin composition
US4614782A (en) Heat resistant resin composition
US3415903A (en) Electrical conductors prepared from polyesters containing tris-(2-hydroxyethyl)-isocyanurate or tris-(2-carboxyethyl)-isocyanurate reacted with polyesteramides
US4319006A (en) Polyamideimide-esterimide heat resistant resin and electric insulating varnish
US3345429A (en) Blended polyester wire enamels and conductors insulated therewith
US20060122353A1 (en) Method of producing a modified diisocyanate,method of producing a self-lubricating enamelling varnish and method of producing an enameled electrical conductor
US4141886A (en) Essentially linear polymer having a plurality of amide, imide, and ester groups therein and a method of making the same
US4224206A (en) Water soluble essentially linear polymer having a plurality of amide, imide and ester groups therein, and a method of making the same and applying the same to substrates
JPS642132B2 (en)
US4459383A (en) Polyamide-imide resin compositions and electrical conductors insulated therewith
US4659622A (en) Essentially linear polymer having a plurality of amide, imide and ester groups therein, a tinnable and solderable magnet wire, and a method of making the same
US4997891A (en) High temperature resistant fast soldering wire enamel
US3389015A (en) Dicyclopentadiene polymer modified polyester wire enamel and varnish
US4611050A (en) Essentially linear polymer having a plurality of amide, imide and ester groups therein, and a method of making the same

Legal Events

Date Code Title Description
AS Assignment

Owner name: SCEHNECTADY CHEMICALS, INC., 2570 BALLTOWN RD., SC

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:SHEN, DENNIS C.;REEL/FRAME:003935/0305

Effective date: 19811012

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, PL 96-517 (ORIGINAL EVENT CODE: M170); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 4

FEPP Fee payment procedure

Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 19901209